Improved coloring material



I Patented Feb. 1, 193a 2 107,159

UNITED STATES PATENT OFFICE.

IMPROVED COLORING MATERIAL 'l'homaoLlhrlonaWilmington. Del, aoalgnor to15.1. du Pont deNemonrs & Company, WilmlngtomDcL, acorporafionofnela NoDrawing. Application November 30, 1934,

Serial No. 755,415

10 Claims. 134-58) This invention relates to improved pigments, ing theradical of a higher alcohol. In'a more lakes and tonersand moreparticularly refers to restricted sense this invention is directed tothe a process for producing insoluble coloring mateformation of superiorcoloring materials by prorial in a much more desirable form than wasduclng said materials in the presence of a water- 5 heretofore possible.soluble salt of a sulfonated alcohol containing at 5 Heretoforepigments, lakes and toners have least 8 carbon atoms. In its preferredembodibeen subject to numerous disadvantages. For exment the presentinvention comprises the formaample, they have been harsh and compact.Upon tion of pigments, lakes and toners in the presence grinding ordrying the yield was appreciably lowof a water-soluble salt of asulfuric acid ester 10 ered and the cost of the resulting products inofa normal primary alcohol containing from 12 10 creased considerably.Light fastness of the reto 18 carbon atoms, and particularly in thepress l in compounds was also frequ tly far from ence of a water-solublesalt of an unsaturated sat sfa t ry. Th st n t s d a d t ture alcoholwhich has been acetylated prior to sulof these compounds were alsounsatisfactory in fonation. 4 many instances. Upon drying these priorart This invention may be more readfly under- 5 products tended to formhard, gritty particles and stood by a consideration of the followingillush r y decrease the strength 01 t y trative examples which, forconvenience, are dipound. when these products were used in the vi t tfollowing la manufacture of printing inks grit and hard particles had tobe completely eliminated to prevent Inorgamc 20 destruction of theprinting plates. In the pro- Lemon yellow chrome lake 2o duction ofrubber colors it was also essential that Iron blue such grit and hardparticles be completely reorganicmoved, particularly when the colorswere imp rt to thin articles. (a) Dis:gic'llucioupling forming insoluble25 It is known that preformed pigments may be treated with certainalcohol derivatives prior to (1) E ;:Z: salt (bronze incorporation intothe materials to be colored.

However, so far as I am aware it has never been (2) Tohudine toner (MNPTbeta suggested that the alcohol derivatives described naphthol) 30hereafter might advantageously be used in pro- (3) B naphthol 2 ammonaph' ducing such pigments. Since my invention is dithalene'l'sulfonicacid rected to the formation of these insoluble colorsoluble dye toinsfluble salt in pres ing materials it is quite distinct from treatment/ence of inorgapic base of such materials after they are formed. The (1)Lithosol rubme BLM 91-183 5 advantages of this invention cannot beobtained (2) Dye corresponding to (3 by suchafter treatment, and thecompounds so Tl'iphenyl methank. treated while their characteristics maybe some- (a) Basic dye to tannic acid lake what improved are,nevertheless, appreciably in- (1) Dye corresponding to 01-729 40 feriorto those produced in accordance with my (b) Basic dye to phosphotungstic-molyb- 40 invention. dig toner It is an object of thisinvention to produce 1 Dye from t t t t pigments, lakes andtoners whichare soft and r r diphenyl ethyl alpha flufiy in texture. A further obect is to prov thybmethane 5 duce insoluble coloring materials whichhave (6) Acid dye to insdluble salt pronounced strength and lightfastness. A still (1) Brilliant blue E c1471 further object is to avoidthe defects previously enumerated with respect to prior art pigments,lakes and toners. Additional objects will become 3. Vat colors- (a)Indigoid and thioindigoid,

(1) Indigo CI-11'7'I P f a n iderat' f th followin 222 ;33 :23 o e g (2)Sulfanthrene pink-FB 01-1211 These objects are attained according to the(b) Anthraqumone herein described invention which comprises (1) P011501blue GD 9 forming pigments, lakes and toners in the pres- Sulful l enceof a sulfonated organic compound contain- (a) Sulfogene blue BXN (fl-95955 IBUI Bull an. term nlhze h 700 cc. water Unit)'llnimlpotaedumfermcnnflemvedln 1000mm Add:

dimeodlumlulfmnltotacemdoduchnloeloleylnlcohol CooltoIO'C.

1000 cc. water mtheeolutlontromunltlmdllnltllntoUnltSatthesameflmeoveroperlodo! minutes. Dflutetomoe. Wuhbtoitlmee,heattoboll. Thenoxldllewlthflznmlenlc chloridethathubeendl-olvodlnmccnter. Wuh,fllteranddry.

Bnonu 0n!" Upper do M 221 I. llthoeol Red 0 bone (2 mm d-sultonlc acid)2000 lbs. voter Paste thoroughly and add:

42.5 lbs. eodlun; hydroxide Heat to 150" 1''. 8thuntll completelydissolved. Then drop into upper tub cont-dining:

MIMI!!! lmlbmm Agltate, then add:

00 lbs. hydrochloric acid 100% ammmmum mmcmu-cmr- -m calm) mthom rlldetubtothemertflmlmm. A lmammal:

umm'mmsmmam two.-

hmpentunlilro. mum. At theeudotthedluotlntlonthendwuldbeapolltlveteettowudetuchlodldepdpere.

Mn thebeto-mphthulct w r. m ceustlc mamrmwmummm. Add maddmomlwllndm.'l'henadd:

30113. 004mm llllhtd It 0! aoetyleted technical Oolorhmdobletom.Thecwpllmwfllnoglomlnthetubu doeatheltnkhtomwlthomnltomtodnloohol.AbmtheoolorombemtedwlthSJ'k moneuflonohdfloohdaflerflmrlnzmdmomentum-1mm lfl'lehllmbeeddedtotheoolorbetoredrylncmdohlghflnldndhomeobtalned MIIA-MAIAMII m wrm mnnn'rnon' (mm mm)7.! put: neh-nltm-nln-tolmdlne (Hthoeol flcdrletlaeel) putedln 7.5portawater. midterm: l'llpu'tlmr. Ooolto32'l". Add:

10.28 m hydrochloric acid (80%) end t0 pub eodmm nltme(100%)d1seolved in38 port water. Dhloflie 1 hour. Add:

0.7! put eodl m M (100%) dissolved in 07.0 m be:

Beta-naphthol 7.6 parts beta-naphthol (100%) 2.25 parts caustic soda(100%) dissolved in 22.5

parts water 2.65 parts soda ash (100%) dissolved in 26.5 parts water.Dissolve and add 1000 parts water at 90 F. Add:

1.0 part sodium sulfate salt of acetylated technical oleyl alcohol Addthe diazo to the naphthol solution. one hour. Wash; filter and dry.

The addition of sulfonated alcohol to the coupling ofmeta-nitro-para-toluidine and betanaphthol produces a toner darker inmasstone, more bronzy, much yellower in shade and much stronger than thestraight coupling.

1.2 parts sodium sulfate salt of technical lauryl alcohol substitutedfor the 1.0 part of corresponding salt of acetylated technical oleylalcohol also produces a toner darker in masstone, more bronzy. yellowerin shade and stronger than the straight coupling. The addition of thissulfonated lauryl alcohol gives a toner slightly lighter in masstone,bluer in shade, and slightly weaker than the toner with sulfonated oleylacetate.

Properties-Alcohol bleeding-straight coupling-bleeds with orangecoloration. Coupling with sodium sulfate salt of acetylated technicaloleyl alcohol'bleeds slightly less than straight coupling. Coupling withsodium sulfate salt of technical lauryl alcohol bleeds slightly lessthan straight coupling and equal to coupling with sulfonated oleylacetate.

Advantages.The sodium sulfate salt of acetylated technical oleyl alcoholused in toluidine toner produces a product impossible to make with thestraight coupling in use at the present time. This is a great advantageas the finished toner is entirely difierent physically from the straighttoner and when made into printing ink has a high glossy finish. Thestrength is also greatly improved making the color of greater value thanthe present types of toluidines.

EXAMPLE 5 BETA NAPHTHOL-YQ-AMINO NAPHTHAIENE-l-SULFONIC Acro Tub 1 30grams beta-naphthol (100%) grams caustic soda (100%) Dissolve thebeta-naphthol in the caustic soda by heating to 140 F. Add 400 cc.water, making Stir ' total volume of 500 cc. Cool this solution to 32 F.with ice. Add enough ice to keep this temperature constant throughoutthe coupling. To the naphthol solution add 40 grams acetic acid (99.5%)and 71.1 grams hydrochloric acid (37.5%). Add the acetic acid, thenafter stirring a few minutes add the hydrochloric acid. Agitate 5minutes. Add 6 grams sodium sulfate salt of acetylated technical oleylalcohol.

Tub 2 45.0 grams 2-amino-naphthalene-l-sulfonic acid is dissolved in 8.8grams caustic soda (10% solution in water) and 250 cc. hot water Make upvolume to about 800 cc. After cooling with ice to 32 F. Add:

13.8 grams sodium nitrite (10% solution in water) to the cooled2-amino-naphthalene-l-sulfonic acid solution Combining 1 and 2 Add the2-amino-naphthalene-l-sulfonic acid solution at 32 F. slowly to thebeta-naphthol suspension at 32 F. Test for sodium nitrite (should be aslight excess by test to starch iodide) Diazotize from 3-5 minutesholding temperature at 32 F. Then add with a medium rapidity:

30 grams, caustic soda (10% solution in water) at 68 F. (100%). Followimmediately by 60 grams barium chloride (10% solution in water) at 68 F.as rapidly as possible. Agitate 10 minutes. Heat to 170 F. slowly.Dilute with water. Stir 4 hours. dry at 130 F.

The coupling with sulfonated alcohol is softer in texture, possessesgreater depth of I masstone, is slightly yellower in shade and shows anincrease of approximately 10% in strength.

EXAIVIPLE 6 Lrrnosor. RUBINE BLM Poworza (IL-183 5 parts lithosol rubineBLM powder suspend in 1000 parts water. Add:

1 part sodium sulfate salt of acetylated technical oleyl alcohol. Heatto 200 F. Hold for 3 minutes. Add:

10 parts acetic acid diluted with 100 parts water.

Add base made as follows:

2026p5uts alum dissolved in 200 parts water at 10 parts soda ashdissolved in 100 parts water at 100 F. Wash free of sulfates. Makevolume up to 400 parts. Precipitate at 140 F. during 4 minutes with 4parts calcium chloride dissolved in 40 parts cold water. Stir one hour,filter and dry.

The above formula gives a finished lake that is softer than the straightprecipitation, is yellower in masstone, yellower in shade and equal instrength. The lake containing sulfonated alcohol bleeds less in alcoholthan the straight precipitation and is non-bleeding in water and oil.

1.2 parts of the sodium sulfate salt of technical lauryl alcohol may besubstituted for the 1 part of sulfonated oleyl acetate and gives a lakeequal in softness, slightly lighter in masstone, slightly bluer in shadeand equal in strength to the straight precipitation.

The lake containing sulfonated lauryl alcohol is darker in masstone, andmuch bluer in shade than the lake containing sulfonated oleyl acetate.It bleeds very slightly more in alcohol than the lake containingsulfonated oleyl acetate and slightly less than the straightprecipitation.

EXAMPLE '7 DYE Oommsronomo 'ro 01-151 10.0 parts alum in 100 parts waterat boil 5.0 parts soda ash in 50 parts water at 100 F. Wash free ofsulfates. Make volume .up to 200 parts with water. Add:

3.0 parts dye corresponding to CI-151 dissolved in 150 parts hot waterto which has been added 0.5 part sodium sulfate salt of acetylatedtechnical oleyl alcohol. Precipitate at 150 F. by adding during 5minutes 3.0 parts barium chloride dissolved in 30 parts water at 150 F.Stir minutes. Wash, filterand dry.

0.6 part sodium sulfate salt of technical lauryl alcohol may besubstituted for the 0.5 part of sulfonated oleyl acetate.

The addition of either of these two agents produces lakes lighter inmasstone, slightly redder in shade and weaker.

The sulfonated oleyl acetate produces a soft fluify lake, much softerthan the straight lake.

EXAMPLE 8 Dn: Comsronnmc 'ro 01-729 1.0 gram dye corresponding to 01-729dissolved in 100 cc. hot water 0.5 cc; glacial acetic acid. Pour ontobase prepared as follows:

20.0 grams alum dissolved in 200 cc. water at 9.0 grams soda ashdissolved in 90 cc. water at 100 F. Wash free of sulfates, make volumeup to 400 cc. Stir 2 minutes. Add:

1.0 gram sodium sulfate salt of acetylated technical oleyl alcohol.Bring to and precipitate at boil with 1.5 grams tannic acid dissolved in15 cc. cold water 0.75 gram tartar emetic dissolved in 15 cc. coldwater. Boil 5 minutes, filter and dry.

1.0 gram sodium sulfate salt of technical lauryl alcohol may besubstituted for the sulfonated oleyl alcohol.

Sulfonated oleyl acetate has an advantage over the straight colorprecipitation in that it is softer, and fluiller and has a much bettertexture. For use in rubber and certain types of ink a product having theabove properties is essential.

EXAIWPLEQ DYE non TIII'BAMPYIHYL-DIAMINO-DIPHENYEETHYL-ALPHA-NAPHTHYL-MD'IHANE 4.0 grams above dye dissolved in 600 cc. waterat the boil. Add

1.0 gram sodium sulfate salt of acetylated technical oleyl alcohol. Addthe following mixture at boil 14.0 grams sodium tungstate in 200 cc.water at boil 2.0 grams sodium molybdate 2.5 grams sodium phosphate 12.8grams hydrochloric acid (20 degrees Be'.)

Wash, filter and dry.

The phosphotungstic-molybdic toner with sulfonated alcohol is a verysoft powder and is very desirable .for use as a rubber color and forprinting inks. Without the use of sulfonated alcohols this desirablephysical form cannot be obtained, so far as is now known.

EXAMPLE Lrrnosor. Barnusn'r Bros: E 01-671 The addition of sulfonatedalcohol produces a very fluffy powder and is weaker in masstone, greenerand brighter in shade and weaker on reduction than the straightprecipitation. However, the lake containing sulfonat'ed alcohol has agreater yield.

The addition of 1.2 parts sodium sulfate salt of technical laurylalcohol in place of the sulfonated acetylated oleyl alcohol givespractically the same masstone and shade but is weaker than the lakecontaining sulfonated oleyl acetate.

EXAMPLE 11 I Imuoo CI-1177 a much better texture, making it moresuitable for use in rubber, inks, etc. than the product obtained withoutthe use of sulfated acetylated technical oleyl alcohol.

(b) Same as above (a) except 1.25 grams sodium salt of sulfatedtechnical lauryl alcohol (mixture of lauryl and myristyl alcohols). Hereagain, improved results were obtained.

(0) An improved pigment can be obtained by adding 1 part sulfatedtechnical cetyl alcohol (based on indoxyl) to the diluted indoxylsolution resulting from the fusion of phenyl glycine with caustic, andoxidizing as usual, with air, sodium hypochlorite or other oxidizingagents.

EXAMPLE 12 SULFANTHBE'NE PINK FB CI-1211 1 gram of sulfanthrene pink FBdouble powder and 3 cc. 31 B. caustic soda are diluted to a volume of200 cc., heated to 70 C. and reduced by the addition of 1.5 grams sodiumhydrosulflte. After the reduction is complete water containing 0.15 gramof the sodium salts of sulfated acetylated technical oleyl alcohol isadded to give a total volume of 400 cc. Air is blown through thesolution at 60 C. until the leuco form of the dye is completelyoxidized. After separation and drying, a product is obtained of improvedphysical properties for use as a pigment.

EXAMPLE 13 PoNsor. BLUE GD 01-1118 4 grams of ponsol blue GD paste and 8cc. 31

.B. caustic. soda are diluted to a volume of 200 cc. heated to 50 C. andreduced by the addition of 1.5 grams sodium hydrosulflte. After thereduction is complete, water containing 0.5 gram of the sodium salt ofsulfated acetylated technical oleyl alcohol is added to give a totalvolume of 400 cc.

Air is blown through the solution at.

50 C. until the leuco form of the dye is com-. pletely oxidized. Afterseparation and drying, a,v

product is obtained which is softer, fluilier and has a much bettertexture, making it more suitable for use as a pigment.

EXAMPLE 14 SULFOGENE BLUE BXN 01-959 containing 1 gram sodium saltsulfated acetylated technical oleyl alcohol are added. Air is blownthrough the solution until the dye is completely precipitated. Afterseparation and drying a product is obtained which is softer, flufllerand actants and the conditions of reaction may be varied within widelimits without departing from the scope of this invention, For example,in place of the various pigments, lakes and toners previously enumeratedor in admixture therewith other insoluble coloring materials may beproduced. The particular method of producing such coloring materials maylikewise vary in accord ance with the class from which such materialsare selected. All prior art processes for producing pigments, lakes andtoners are contemplated as coming within the scope of this inventionwhen modified by conducting such processes in the presence of sulfonatedorganic compounds containing the radical of a higher alcohol. Suchsulfonated organic compound may be added to any one of the constituentsor to the reaction mixture-prior to formation of the ultimate insolublecoloring material.

Sulfonated organic compounds which are capable of use herein areexceedingly numerous and may be used either alone, in admixture with oneanother and/or in admixture with assistants previously used in the priorart for producing pigments, lakes and/or toners. These compounds must,in general, contain the radical of a higher alcohol. The particularalcohol, the radical of which is contained in such compound, may beselected from various classes such as the aliphatic, hydrocyclic oraralkyl series. Most satisfactory results are, in general, obtained byselecting normal primary alcohols having at least 8 carbon atoms andpreferably from 12 to 18 carbon atoms in the molecule. Alcohols comingwithin the aforementioned category are: octyl, decyl, lauryl, myristyl,cetyl, stearyl, oleyl, ricinoleyl, linoleyl, batyl, selachyl, chimyl,etc.

alcohols. The alcohols suitable for use herein may be unsaturated and/orpolyhydric. Furthermore, they may contain additional substituents suchas chlorine and other halogen groups, alkoxy groups, acyl, borate, etc.groups. Acetylated unsaturated normal primary alcohols, in particularacetylated oleyl alcohol, have been found to give excellent results forthis purpose. Such compounds may, for example, be produced by treatingoleyl or other unsaturated alcohols with acetic anhydride.

The aforementioned or related alcohols may be treated with sulfonatingagents such as concentrated sulfuri acid, oleum, pyridine-sulfurtrioxide, sodium pyrosulfate, amino-sulfonic acid, imino-disulfonicacid, aryl sulfamic acid, and chlorsulfonic acid. In this connection, itmay be mentioned that where sulfonation is referred to herein it is usedin the generic sense to mean either the production of a sulfuric acidester or the production of a true sulfonic acid derivative. Sincesulfuric acid esters are ordinarily superior to the true sulfonic acidderivatives it is advisable to carry out the sulfonation under suchconditions that they will be produced. This may frequently beaccomplished by conducting the sulfonation within the temperature rangeof 0-50 C.

Sulfonated derivatives of the alcohols, produced in accordance with theaforementioned instructions, are advisably neutralized with saltformingcompounds. These compounds may be of either inorganic or organic origin.Examples of a few salt-forming compounds of inorganic origin are soda.ash, caustic soda, ammonium hydroxide, caustic potash, oxides andhydroxides of calcium, magnesium, lithium, etc. Among the salt-formingcompounds of organic origin mention may be made of the aromatic amines,quaternary ammonium bases, cyclohexylamines, monoanddi-cyclohexylamines, quarternary phosphonium bases, tertiary sulfoniumbases, alicyclic hydroxy amino compounds, pyridine, piperidine, mono-,diand tri-alkylamines, mono-, diand tri-alkylolamines, etc.

In place of the above mentioned sulfonated alcohols or mixtures thereofadditional derivatives are contemplated for use herein. For exmay bereacted with the sulfonating agent. Ex-. amples of such compounds aresulfonated glycerol ethers of lauryl, myristyl, cetyl, stearyl, oleyl,etc. alcohols.

The amount of the sulfonated organic compound which may be used inaccordance herewith may vary widely depending upon the particularcoloring materials which are to be formed. In general, amounts varyingfrom a few hundredths of one per cent to three per cent, based upon theweight of pigment, lake or toner, are satisfactory. However, it is notintended to restrict this invention to any particular amount since theoptimum quantity for any given product may be easily determined byconducting a few routine experiments.

By means of the present invention pigments,

- lakes and toners having a soft flufiy texture are produced. The.strength and light fastness of these compounds is markedly superior tothose produced in accordance with prior art methods. These products arequite dissimilar physically to those heretofore known and may ordinarilybe used in much smaller quantities than was previously possible. Suchproducts have a variety of uses, for example in the production ofprinting inks, colored rubber materials, etc. They may be used in any ofthe processes wherein prior art pigments, lakes and toners have beenused or are capable of use. Likewise, they may be used in adsolublesulfate of an acetyiated, unsaturated, normal, primary alcohol havingtwelve to eighteen carbon atoms in the molecule and both of saidsolutions being free from emulsified oils.

2. A process for producing unimproved waterinsoluble pigment whichcomprises admixing an aqueous solution of an organic dyestufi or anorganic dyestuii' intermediate with another aque-. ous solution whichcontains a compound capable of reacting with said dvestufi or dyestufiintermediate to form said pigment without subsequent oxidation, one ofsaid solutions containing a water-soluble sulfate of an acetylated,unsaturated, normal, primary alcohol having twelve to eighteen carbonatoms in the molecule and both of said solutions being free fromemulsified oils.

3. A process for producing an improved azo pigment which comprisesadmixing an'aqueous solution of a diaaotiaed aryl amine with an aqueoussolution of a coupling component which contains a water-soluble sulfateof an acetylated, unsaturated, normal, primary alcohol having twelve toeighteen carbon atoms in the molecule, both of said solutions being freefrom emulsified oils.

4. A process for producing an improved azo pigment which comprisesadmixing an aqueous idine toner which comprises admixing a solutioncontaining diazotiaed meta-nitro-para-toluidine with an aqueous solutioncontaining beta naphthol and the sodium sulfate salt of aoetylatedtechnical oleyl alcohol, both of said solutions being free fromemulsified oils.

7. A process for producing an improved waterinsoluble pigment whichcomprises admixing aqueous solutions of two compounds which reactwithout an oxidation step to form said pigment, one of said solutionscontaining the sodium sulfate salt of acetylated technical oleyl alcoholand both of said solutions being free from emulsified oils.

8. A process for producing an improved waterinsoluble pigment whichcomprises admixing an aqueous solution of an organic dyestufi' or anorganic dyestufi intermediate with another aqueous solution whichcontains a compound capable of reacting with said dyestufi. or dyestufi!intermediate to form said pigment without subsequent oxidation, one ofsaid solutions containing the sodium sulfate salt of acetylatedtechnical oleyl alcohol and both of said solutions being free fromemulsified oils.

9 A process for producing an improved 8 0 pigment which comprisesadmixing an aqueous solution of a diazotized aryl amine with an aqueoussolution of a coupling component which contains the sodium sulfate saltof acetylated technical oleyl alcohol, both of said solutions being freefrom emulsified oils.

10. A process for producing an improved azo pigment which comprisesadmixing an aqueous solution of a diazotized aryl amine with an aqueoussolution containing beta naphthol and the sodium sulfate salt ofacetylated technical 'oleyl alcohol, both of said solutions being freefrom emulsified oils.

THOMAS A. MAR'IONE.

